JPH02172713A - Injection molding process for rubber product - Google Patents
Injection molding process for rubber productInfo
- Publication number
- JPH02172713A JPH02172713A JP63330016A JP33001688A JPH02172713A JP H02172713 A JPH02172713 A JP H02172713A JP 63330016 A JP63330016 A JP 63330016A JP 33001688 A JP33001688 A JP 33001688A JP H02172713 A JPH02172713 A JP H02172713A
- Authority
- JP
- Japan
- Prior art keywords
- rubber
- injection
- injection molding
- rubber compound
- pts
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920001971 elastomer Polymers 0.000 title claims abstract description 65
- 239000005060 rubber Substances 0.000 title claims abstract description 65
- 238000001746 injection moulding Methods 0.000 title claims description 15
- 150000001875 compounds Chemical class 0.000 claims abstract description 29
- 239000003795 chemical substances by application Substances 0.000 claims abstract description 9
- 238000010058 rubber compounding Methods 0.000 claims abstract description 5
- 238000002347 injection Methods 0.000 claims description 17
- 239000007924 injection Substances 0.000 claims description 17
- 239000006087 Silane Coupling Agent Substances 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- 238000005299 abrasion Methods 0.000 abstract description 5
- 238000007906 compression Methods 0.000 abstract description 5
- 230000006835 compression Effects 0.000 abstract description 5
- 239000000463 material Substances 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 abstract 2
- 239000007822 coupling agent Substances 0.000 abstract 2
- 238000004073 vulcanization Methods 0.000 description 14
- 238000000465 moulding Methods 0.000 description 8
- 239000000203 mixture Substances 0.000 description 5
- 239000000945 filler Substances 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- -1 and if necessary Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000009472 formulation Methods 0.000 description 2
- 239000003607 modifier Substances 0.000 description 2
- 229920002857 polybutadiene Polymers 0.000 description 2
- RMAQACBXLXPBSY-UHFFFAOYSA-N silicic acid Chemical compound O[Si](O)(O)O RMAQACBXLXPBSY-UHFFFAOYSA-N 0.000 description 2
- 235000012239 silicon dioxide Nutrition 0.000 description 2
- 244000043261 Hevea brasiliensis Species 0.000 description 1
- 229920000459 Nitrile rubber Polymers 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- 230000003712 anti-aging effect Effects 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000004040 coloring Methods 0.000 description 1
- 229920003244 diene elastomer Polymers 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000004088 foaming agent Substances 0.000 description 1
- 239000002932 luster Substances 0.000 description 1
- 230000013011 mating Effects 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 229920003052 natural elastomer Polymers 0.000 description 1
- 229920001194 natural rubber Polymers 0.000 description 1
- 238000012856 packing Methods 0.000 description 1
- 239000008188 pellet Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 239000004014 plasticizer Substances 0.000 description 1
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000003381 stabilizer Substances 0.000 description 1
- 229920003048 styrene butadiene rubber Polymers 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 229920001169 thermoplastic Polymers 0.000 description 1
- 239000004416 thermosoftening plastic Substances 0.000 description 1
- 230000000007 visual effect Effects 0.000 description 1
Landscapes
- Footwear And Its Accessory, Manufacturing Method And Apparatuses (AREA)
- Moulds For Moulding Plastics Or The Like (AREA)
- Injection Moulding Of Plastics Or The Like (AREA)
- Molding Of Porous Articles (AREA)
Abstract
Description
【発明の詳細な説明】
（産業上の利用分野）
この発明は、ゴム製品の射出成形法に関するものである
。DETAILED DESCRIPTION OF THE INVENTION (Industrial Application Field) This invention relates to an injection molding method for rubber products.
（従来の技術）
従来、履物分野、バッキング、防振ゴム等の工業用品分
野において、ゴム配合物をモールドキャビティに射出充
填して、これを加熱加硫してゴム製品を射出成形する方
法は文献上一般に良く知られている。しかしながらゴム
製品の射出成形において、加熱加硫する工程が必要であ
るため一般の熱可塑性合成樹脂の射出成形に比較して成
形能率が著しく低下するため、ゴムの射出成形はこれら
の分野においてはまだ汎用なものとはなっていないのが
現状である。ゴムの射出成形において加硫時間を短縮さ
せるためには、ゴム配合物中に加硫促進剤と加硫剤を通
常以上に増量して添加しておくか、加硫温度を２００℃
以上に設定することも考えられるが、加硫促進剤と加硫
剤の増量による場合、ゴム配合物を射出シリンダーで可
塑化する段階で、ゴム配合物がスコーチを起し射出不能
となり、また加硫温度を高く設定すると成形されるゴム
製品の引っ張り強度が著しく低下し、しかも永久歪が大
きくなる欠点がある。(Prior Art) Conventionally, in the field of footwear, backings, anti-vibration rubber, and other industrial products, there is a method of injection-molding rubber products by injecting and filling a rubber compound into a mold cavity and heating and vulcanizing the mixture. The above is generally well known. However, the injection molding of rubber products requires a heat vulcanization process, which significantly lowers the molding efficiency compared to the injection molding of general thermoplastic synthetic resins, so rubber injection molding is still underdeveloped in these fields. The current situation is that it is not a universal product. In order to shorten the vulcanization time in rubber injection molding, either add a vulcanization accelerator and a vulcanizing agent to the rubber compound in larger amounts than usual, or increase the vulcanization temperature to 200°C.
It is possible to set the above value, but if the amount of vulcanization accelerator and vulcanizing agent is increased, the rubber compound will scorch during the plasticization stage of the rubber compound in the injection cylinder, making it impossible to inject. If the sulfur temperature is set high, the tensile strength of the molded rubber product will drop significantly and permanent deformation will increase.
従って、特許出願人は先に特公昭５７−２２９４４号に
よって１．２ポリブタジ工ン１００重量部に対して、ジ
エン系ゴム５〜９０重量部を常用ゴム配合薬品とともに
添加したゴム配合物を１００°Ｃの射出温度でモールド
キャビティに射出充填し、これを１８０℃で加硫する靴
底の射出成形法を提案した。Therefore, the patent applicant previously proposed in Japanese Patent Publication No. 57-22944 that 100° We proposed an injection molding method for shoe soles in which the mold cavity is injected and filled at an injection temperature of C and vulcanized at 180C.
しかしながらこのようにして成形された靴底は、ゴム配
合物が射出成形時に過剰な流動性を示すため、モールド
の成形面に滑り止め意匠等の凹凸が形成されている場合
は、ゴム配合物が凹凸意匠に激突し、凹凸面にエアを巻
き込み、これが接地面に封入されて成形される靴底の接
地面に欠けが形成され外観が著しく低下したり、また金
型の合せ面にゴム配合物が流入固化してパリが形成され
、成形後パリを除去しなければならず、多大の労力を必
要としていた。However, in the soles molded in this way, the rubber compound exhibits excessive fluidity during injection molding, so if the molding surface of the mold has irregularities such as a non-slip design, the rubber compound may When the bumps collide with the uneven design, air is drawn into the uneven surface, and this air is trapped in the contact surface of the shoe sole to form chips, which significantly deteriorates the appearance.Also, if there is no rubber compound on the mating surface of the mold. The material flows in and solidifies, forming a barrier, which must be removed after molding, which requires a great deal of labor.
（発明の解決しようとする問題点）
この発明は成形時にパリが形成されることがなく、外観
良好で引っ張り強度、耐摩耗性等の機械的強度に優れ、
圧縮永久歪の小さなゴム製品を能率的に射出成形しよう
とするものである。(Problems to be Solved by the Invention) This invention does not form flakes during molding, has a good appearance, and has excellent mechanical strength such as tensile strength and abrasion resistance.
The objective is to efficiently injection mold rubber products with low compression set.
（問題点を解決するための手段）
この発明は、ゴム１００重量部にシラン系カップリング
剤１〜７重量部と加硫剤とその他の常用ゴム配合薬品と
を添加したゴム配合物を射出温度９０℃〜１３０℃でモ
ールドキャビティに射出充填し、これを１３０℃〜１９
０℃で加熱して加硫することを特徴とするゴム製品の射
出成形法を発明の要旨とするものである。(Means for Solving the Problems) This invention provides a rubber compound in which 1 to 7 parts by weight of a silane coupling agent, a vulcanizing agent, and other commonly used rubber compounding chemicals are added to 100 parts by weight of rubber at injection temperature. The mold cavity is injected and filled at 90°C to 130°C.
The gist of the invention is an injection molding method for rubber products characterized by heating and vulcanization at 0°C.
この発明において、ジエン系ゴムとしては、例えば天然
ゴム、スチレンブタジェンゴム、ポリブタジェンゴム、
アクリロニトリルブタジェンゴム等の一種または二種以
上を組合せたものが使用される。In this invention, examples of the diene rubber include natural rubber, styrene-butadiene rubber, polybutadiene rubber,
One type or a combination of two or more types of acrylonitrile butadiene rubber can be used.
この発明において、シラン系カップリング剤としては、
例えば（トリメトキシリル−メチル）オリゴスルファイ
ド、ビス−（トリニドキシリル−メチル）オリゴスルフ
ァイド、ビス−（トリプロポキシリル−メチル）オリゴ
スルファイド、ビス−（トリブトホキシリル−メチル）
オリゴスルファイド、ビス−（２−トリル−メトキシリ
ル−エチル）オリゴスルファイド、ビス−（２−トリー
ニドキシリル−エチル）オリゴスルファイド、ビス−（
２−トリプロポキシリル−エチル）オリゴスルファイド
、ビス−（２−トリプトキシリル−エチル）オリゴスル
ファイド、ビス−（３−トリメトキシリル−プロピル）
オリゴスルファイド、ビス−（３−トリニドキシリル−
プロピル）オリゴスルファイド、ビス−（３−トリプポ
キシリループロビル）オリゴスルファイド、ビス−（３
−トリーｎ−ブトキシリル）オリゴスルファイド等のビ
ス−（トリアルコキシリル−アルキル）オリゴスルファ
イドが使用される。In this invention, the silane coupling agent is
For example (trimethoxylyl-methyl) oligosulfide, bis-(trinidoxylyl-methyl) oligosulfide, bis-(tripropoxylyl-methyl) oligosulfide, bis-(tributoxylyl-methyl)
Oligosulfide, bis-(2-tolyl-methoxylyl-ethyl)oligosulfide, bis-(2-trinidoxylyl-ethyl)oligosulfide, bis-(
2-tripropoxylyl-ethyl) oligosulfide, bis-(2-triptoxylyl-ethyl) oligosulfide, bis-(3-trimethoxylyl-propyl)
Oligosulfide, bis-(3-trinidoxylyl-
propyl) oligosulfide, bis-(3-trypoxylyluprovir) oligosulfide, bis-(3
Bis-(trialkoxylyl-alkyl)oligosulfides such as -tri-n-butoxylyl)oligosulfides are used.
この発明において、ゴム混合物１００重量部に対して、
シラン系カップリング剤の添加量を１〜７重量部に限定
したのは、添加量がそれ以下となれば、射出成形時の流
動性が低下し、成形されるゴム製品の表面肌が荒れ、光
沢を失い極端な場合は、モールドキャビティに対する充
填不足を生じ、ゴム製品の表面が欠けて商品価値を失う
欠点があり、また添加量がそれ以上となれば、コストが
著しくアップし、しかもそれ以上の改良効果がみられな
いからである。In this invention, based on 100 parts by weight of the rubber mixture,
The reason why the amount of silane coupling agent added is limited to 1 to 7 parts by weight is that if the amount added is less than that, the fluidity during injection molding will decrease and the surface of the molded rubber product will become rough. In extreme cases of loss of luster, the mold cavity may be insufficiently filled, and the surface of the rubber product may be chipped, resulting in a loss of commercial value.Additionally, if the amount added is greater than that, the cost will increase significantly; This is because no improvement effect was observed.
さらにこの発明において、ゴム配合物中に充填剤として
シリカ等のケイ酸系充填剤をゴム１００重量部に対して
３０〜６０重量部添加しておけば、シラン系カップリン
グ剤とケイ酸系充填剤とゴムの化学的結合によって、成
形されるゴム製品の引っ張り強度、耐摩耗性、圧縮永久
歪等の機械的強度のより一層の改善を図ることができる
。Furthermore, in this invention, if 30 to 60 parts by weight of a silicic acid filler such as silica is added to the rubber compound as a filler per 100 parts by weight of rubber, the silane coupling agent and the silicic acid filler can be combined with each other. By chemically bonding the agent and rubber, it is possible to further improve mechanical strengths such as tensile strength, abrasion resistance, and compression set of the molded rubber product.
この発明において使用されるその他の常用ゴム配合薬品
としては、加硫助剤、加硫促進剤、充填剤さらに必要に
応じて可塑剤、軟化剤、発泡剤、発泡助剤、着色顔料、
老化防止剤。Other common rubber compounding chemicals used in this invention include vulcanization aids, vulcanization accelerators, fillers, and if necessary, plasticizers, softeners, foaming agents, foaming aids, coloring pigments,
Anti-aging agent.
安定剤等が添加配合される。Stabilizers and the like are added and blended.
さらにこの発明において、改良剤として１．２ポリブタ
ジエンをゴム１００重量部に対して、５〜２５重量部添
加配合しておけば、成形性を阻害することなく、成形さ
れるゴム製品の重量を軽減し、しかもゴム製品の硬度を
高めることができるので好都合である。Furthermore, in this invention, if 5 to 25 parts by weight of 1.2 polybutadiene is added as a modifier to 100 parts by weight of rubber, the weight of the rubber product to be molded can be reduced without impeding moldability. Moreover, it is advantageous because the hardness of the rubber product can be increased.
以上のようにして準備された材料は、パンパリミキサー
、混線ロール、ニーダ等の公知の装置によって配合混練
され、シーテングされ、必要によってさらにペレット状
、リボン状等の細片に裁断され、ゴム製品の射出成形用
のゴム配合物として提供され、そして通常のゴム用の射
出成形機によってモールドキャビティに射出導入して加
硫されるものである。The materials prepared as described above are compounded and kneaded using known equipment such as a Pampari mixer, mixed wire roll, kneader, etc., sheeted, and further cut into pellets, ribbons, etc., if necessary, to form rubber products. It is provided as a rubber compound for injection molding, and is injected into a mold cavity by a conventional rubber injection molding machine and vulcanized.
この発明において、ゴム配合物の射出温度（射出ノズル
から吐きだされる時のゴム配合物の温度）を９０℃〜１
３０℃に限定したのは、射出温度がそれ以下となれば、
ゴム配合物のモールドキャビティ中での型流れ性が低下
し、成形されるゴム製品が欠ける欠点があり、また射出
温度がそれ以上となれば、ゴム配合物がランナー、ゲー
トを通過する際、ゴム配合物にさらに摩擦熱が付加され
、ゴム配合物中ランナー、ゲート中で部分的に加硫、即
ち、ゴム配合物がスコーチし、モールドキャビティに対
する射出充填が不可能になったり、モールドキャビティ
でのゴム配合物の型流れ性が低下し、成形されるゴム製
品が欠けたりする欠点があるからである。In this invention, the injection temperature of the rubber compound (the temperature of the rubber compound when it is discharged from the injection nozzle) is set at 90°C to 1°C.
The reason why we limited it to 30℃ is that if the injection temperature is lower than that,
There is a disadvantage that the mold flowability of the rubber compound in the mold cavity decreases, resulting in chipping of the molded rubber product.In addition, if the injection temperature is higher than this, the rubber compound may deteriorate when it passes through the runner and gate. Further frictional heat is added to the compound and the rubber compound is partially vulcanized in the runners and gates, i.e. the rubber compound is scorched, making injection filling into the mold cavity impossible or causing the mold cavity to vulcanize. This is because the mold flowability of the rubber compound is reduced and the molded rubber product may be chipped.
（発明の作用効果）
この発明は以上のように構成されており、成形時にパリ
が形成されることがなく、外観良好で引っ張り強度、耐
摩耗性、圧縮永久歪を改善したゴム製品を短時間加硫に
よって能率的に成形できた。(Operations and Effects of the Invention) This invention is configured as described above, and can produce rubber products in a short period of time without the formation of flakes during molding, with good appearance, and improved tensile strength, abrasion resistance, and compression set. It could be efficiently molded by vulcanization.
この原因として、ゴム配合物中に添加されたシラン系カ
ップリング剤中のメチル、エチル、プロピル等のアルキ
ル基が作用して、射出成形におけるゴム配合物は、射出
シリンダーノズル、ランナー、スプルー、モールドキャ
ビティで可塑化され流動性が促進される。The cause of this is that alkyl groups such as methyl, ethyl, and propyl in the silane coupling agent added to the rubber compound act, and the rubber compound in injection molding is It is plasticized in the cavity and fluidity is promoted.
即ち、可塑化流動段階ではシラン系カップリング剤がゴ
ム配合物に良好な流動性を付与する。従って可塑化流動
段階でゴム配合物がスコーチを引き起すことがない。モ
ールドキャビティ中での加硫段階では、シラン系カップ
リング剤中のオリゴスルファイド基が作用してゴム配合
物は、流動性を急激に抑制され、その加硫を促進するた
めセルフパツキン材となりパリが形成されることがない
。それ故に通常の加硫温度で高物性のゴム製品が短時間
にパリ無しで成形加硫されると考えられる。That is, in the plasticization flow stage, the silane coupling agent imparts good fluidity to the rubber compound. Therefore, the rubber compound does not cause scorch during the plasticization flow stage. During the vulcanization stage in the mold cavity, the oligosulfide groups in the silane coupling agent act to rapidly suppress the fluidity of the rubber compound, and in order to promote vulcanization, it becomes a self-packing material. is never formed. Therefore, it is thought that rubber products with high physical properties can be molded and vulcanized without flashing in a short time at normal vulcanization temperatures.
以上のごとく、ゴム配合物中のシラン系カップリング剤
が成形の初期の流動性を必要とする時は流動性改質剤と
なり、成形の後期においては急激な加硫剤となり、流動
性を抑止し加硫を促進するものと考えられる。As mentioned above, the silane coupling agent in the rubber compound acts as a fluidity modifier when fluidity is required in the early stages of molding, and acts as a rapid vulcanizing agent in the later stages of molding, suppressing fluidity. This is thought to promote vulcanization.
（実施例）
第１表、実施例１〜４に示す配合のゴム配合をバンバリ
ーミキサ−によって混練し、厚み９−にシーテングし、
さらにこれをリボン状に裁断したゴム配合物を、西独デ
スマ社 デスマフ３１−１２ステーシヨンラバー、イン
ジェクションマシンを使用して、予め胛被を吊込みセッ
トした靴底成形キャビティに射出圧１０００ｋｇ／、ｆ
ｆｌ、射出温度１２０℃で射出充填した後、これを１７
５℃で加熱して加硫して肉厚６１Ｔｆｆｌのゴム靴底を
有する靴を成形した。(Example) The rubber compositions shown in Table 1 and Examples 1 to 4 were kneaded using a Banbury mixer, and sheeted to a thickness of 9 mm.
Furthermore, the rubber compound cut into ribbons was injected into a shoe sole molding cavity in which a shoe cover had been suspended and set in advance using a Desmuff 31-12 station rubber injection machine manufactured by Desmas, with an injection pressure of 1000 kg/f.
fl, after injection filling at an injection temperature of 120°C, this was
The product was heated and vulcanized at 5° C. to form a shoe having a rubber sole with a wall thickness of 61 Tffl.
これを比較例の配合によって射出されるゴム配合物の射
出時（射出ノズルから吐き出される時）のゴム配合物の
ムニー粘度並びにモールドキャビティ中での加硫速度、
さらに比較例の配合によって射出成形されたゴム靴底と
その外観、引っ張り強度、耐摩耗性、圧縮永久歪、重量
比を比較して第２表に示す。第１表下段に示すようにこ
の発明によって得られたゴム靴底は本発明所望のもので
あった。This is the Muni viscosity of the rubber compound injected according to the formulation of the comparative example at the time of injection (when it is discharged from the injection nozzle), the vulcanization rate in the mold cavity,
Further, Table 2 shows a comparison of the appearance, tensile strength, abrasion resistance, compression set, and weight ratio of rubber shoe soles injection molded using the formulation of the comparative example. As shown in the lower row of Table 1, the rubber soles obtained according to the present invention were the ones desired by the present invention.
×０ 目視評価
ｍｌ ＪＩＳ Ｋ６３０１法による単位ｋｇ／１ｆ
ｆｌ※２ ＪＩＳ Ｋ６３０１法による単位％（７
０℃ｘ ２２Ｈ）※３ アクロン式荷重５．０ｋｇ、角
度１５″、予備槽１０００回。×0 Visual evaluation ml Unit kg/1f according to JIS K6301 method
fl*2 Unit % according to JIS K6301 method (7
0℃ x 22H) *3 Akron type load 5.0kg, angle 15'', preliminary tank 1000 times.
本摺３３００回、単位ωHonzuri 3300 times, unit ω
Claims (1)
量部と加硫剤とその他の常用ゴム配合薬品とを添加した
ゴム配合物を射出温度９０℃〜１３０℃でモールドキャ
ビティに射出充填し、これを１３０℃〜１９０℃で加熱
して加硫することを特徴とするゴム製品の射出成形法。A rubber compound obtained by adding 1 to 7 parts by weight of a silane coupling agent, a vulcanizing agent, and other commonly used rubber compounding chemicals to 100 parts by weight of rubber is injected and filled into a mold cavity at an injection temperature of 90°C to 130°C, An injection molding method for rubber products, which is characterized by heating and vulcanizing the product at 130°C to 190°C.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63330016A JPH02172713A (en) | 1988-12-26 | 1988-12-26 | Injection molding process for rubber product |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP63330016A JPH02172713A (en) | 1988-12-26 | 1988-12-26 | Injection molding process for rubber product |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH02172713A true JPH02172713A (en) | 1990-07-04 |
| JPH0536213B2 JPH0536213B2 (en) | 1993-05-28 |
Family
ID=18227832
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP63330016A Granted JPH02172713A (en) | 1988-12-26 | 1988-12-26 | Injection molding process for rubber product |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02172713A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11103903A (en) * | 1997-10-07 | 1999-04-20 | Sumitomo Rubber Ind Ltd | Shoes |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5722944A (en) * | 1980-07-14 | 1982-02-06 | Mitsubishi Electric Corp | Vehicle accident preventing device |
| JPS63128037A (en) * | 1986-11-18 | 1988-05-31 | Ube Ind Ltd | Passenger car tire |
| JPS63311970A (en) * | 1987-06-12 | 1988-12-20 | 株式会社アシックス | Solid golf ball |
-
1988
- 1988-12-26 JP JP63330016A patent/JPH02172713A/en active Granted
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5722944A (en) * | 1980-07-14 | 1982-02-06 | Mitsubishi Electric Corp | Vehicle accident preventing device |
| JPS63128037A (en) * | 1986-11-18 | 1988-05-31 | Ube Ind Ltd | Passenger car tire |
| JPS63311970A (en) * | 1987-06-12 | 1988-12-20 | 株式会社アシックス | Solid golf ball |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPH11103903A (en) * | 1997-10-07 | 1999-04-20 | Sumitomo Rubber Ind Ltd | Shoes |
Also Published As
| Publication number | Publication date |
|---|---|
| JPH0536213B2 (en) | 1993-05-28 |
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